ABSTRACT
Defect engineering, such as modification of oxygen vacancy density, has been considered as an effective approach to tailor the catalytic performance on transition-metal oxide nanostructured surfaces. The role of oxygen vacancies (OV) on the surface of the as-prepared, zinnia-shaped morphology of CuO nanostructures and their marigold forms on calcination at 800 °C has been investigated through the study of model catalytic reactions of reduction of 4-nitrophenol and aerobic oxidation of benzyl alcohol. The OV on the surfaces of different morphologies of CuO have been identified and quantified through Rietveld analysis and HRTEM, EPR, and XPS studies. The structure-activity relationships between surface oxygen vacancies (OV) and catalytic performance have been systematically investigated. The enhanced catalytic performance of the cubic CuO nanostructures compared to their as-prepared forms has been attributed to the formation of surface oxygen species on the reactive and dominant (110) surface that has low oxygen vacancy formation energy. The mechanistic role of surface oxygen species in the studied reactions has been quantitatively correlated with the catalytic activity of the different morphological forms of the CuO nanostructures.